Our invention relates to oral sensory perception-affecting compositions containing dimethyl sulfoxide, complexes thereof and salts thereof, specifically comprising (i) dimethyl sulfoxide and (ii) a second compound or group of compounds:
(a) containing at least one menthyl moiety; and/or
(b) containing at least one vanillyl moiety; and/or
(c) containing at least one carboxamide moiety.
The term xe2x80x9coral sensory perception-affecting compositionsxe2x80x9d is intended to cover xe2x80x9ccoolant compositionsxe2x80x9d as well as xe2x80x9cheat compositions.xe2x80x9d
Compositions containing compounds producing a cooling sensation, specifically hydroxy methyl or hydroxy ethyl derivatives of paramenthane are disclosed in U.S. Pat. No. 4,029,759. Such compositions are disclosed to be useful, for example, for spearmint flavor used in toothpastes, as well as other ingestible materials such as margarine and the like. Breath freshening edible compositions of menthol and a carboxamide are disclosed in U.S. Pat. No. 5,009,893. xe2x80x9cHot, tingling, burning, numbingxe2x80x9d causing sensations by use of 4-(1-menthoxymethyl)-2-phenyl-1,3-dioxolane or a derivative thereof is disclosed in U.S. Pat. No. 5,545,424 issued on Aug. 13, 1996. Combinations of coolant compositions comprising a ketal and a secondary coolant which may be menthol are disclosed in PCT Application No. 93/23005 published on Nov. 25, 1993. Production of chewing gum containing controlled release acyclic carboxamides as cooling agents are disclosed in PCT Application No. 99/13870 published on Mar. 25, 1999. Chewing gum production using modified, physiological cooling agents, to wit: menthol, menthone and a carboxamide or a ketal or a diol or a succinate or mixtures of same, are disclosed in PCT Application No. 99/13734 published on Mar. 25, 1999.
However, there exists an ongoing need to provide enhancement of such xe2x80x9chotxe2x80x9d sensations or such xe2x80x9ccoolingxe2x80x9d sensations in various edible compositions, including beverages, toothpastes, throat lozenges, mouthwashes, dental floss, chewing gums, edible films such as breath freshener films and chewable pharmaceutical products, particularly wherein such xe2x80x9cenhancementxe2x80x9d raises the level of the xe2x80x9chotxe2x80x9d or xe2x80x9ccoolingxe2x80x9d sensation on ingestion of the edible composition, on a scale of 0-10, from about 2 up to about 10. The provision of such enhancement properties has heretofore been unknown and not implied in any prior art. Accordingly, nothing in the prior art sets forth the use of combinations of dimethyl sulfoxide with compounds containing at least one menthyl moiety, compounds containing at least one vanillyl moiety and/or compounds containing at least one carboxamide moiety in order to enhance oral sensory perception, including xe2x80x9chotxe2x80x9d sensations and xe2x80x9ccoolxe2x80x9d sensations.
Indeed, the use of dimethyl sulfoxide in foodstuffs and the presence of dimethyl sulfoxide in foodstuffs is well known. Thus, dimethyl sulfoxide is set forth in the TNO Nutrition and Food Research Institute""s Volatile Compounds in Food/Qualitative and Quantitative Data, Seventh Edition 1996 (Editors: L. M. Nijssen, et al.) at page 8 under CAS No. 67/68/5. Dimethyl sulfoxide is also on the GRAS list as published in GRAS Flavoring Substances 18, the 18th publication by the Flavor and Extract Manufacturers"" Association""s Expert Panel on recent progress in the consideration of the flavoring ingredients generally recognized as safe for use in food (reference: Cooked Food Technology, September 1998, Volume 52, No. 9 (GRAS No. 3875)) (also called xe2x80x9cmethyl sulfoxide,xe2x80x9d xe2x80x9cDMSOxe2x80x9d and xe2x80x9cmethyl sulfinyl methane.xe2x80x9d Nothing in the prior art discloses the effect of dimethyl sulfoxide on other sensory affecting agents, particularly oral sensory perception-affecting compositions such as coolant compositions or xe2x80x9chot, burning, bitterxe2x80x9d compositions.
Our invention is directed to oral sensory perception-affecting compositions containing dimethyl sulfoxide, complexes thereof and salts thereof, specifically comprising:
(i) dimethyl sulfoxide having the structure: 
(ii) a second compound or group of compounds:
(a) containing at least one menthyl moiety; and/or
(b) containing at least one vanillyl moiety; and/or
(c) containing at least one carboxamide moiety,
wherein the weight ratio of xe2x80x9csecond compound(s)xe2x80x9d:dimethyl sulfoxide, is in the range of from about 1,000:1 down to about 3:1 and food grade acceptable salts thereof.
Our invention also covers oral sensory perception-affecting compositions (e.g., xe2x80x9ccoolantsxe2x80x9d)-imparting consumable articles (e.g., beverages, toothpastes, throat lozenges, mouthwashes, dental floss, chewing gums, edible films and chewable pharmaceutical products). The sensory-affecting consumable articles having intensified and substantive sensory-affecting properties such as oral cooling properties and oral heating properties comprise (i) an ultimate product base and intimately admixed therewith (ii) a composition comprising (a) dimethyl sulfoxide and (b) a second compound or mixture of compounds selecting from the group consisting of compounds:
(a) containing at least one menthyl moiety; and/or
(b) containing at least one vanillyl moiety; and/or
(c) containing at least one carboxamide moiety
wherein the weight ratio of second compound or group of compounds:dimethyl sulfoxide, is in the range of from about 1,000:1 down to about 3:10 and food grade acceptable salts thereof, wherein the concentration of dimethyl sulfoxide based on the weight of ultimate product is from about 0.05 up to about 200 parts per million (ppm) and the concentration of second compound or group of compounds or mixture of compounds is from about 2 ppm up to about 10,000 ppm on a mixed basis.
Examples of the xe2x80x9csecond compoundxe2x80x9d to be admixed with the dimethyl sulfoxide forming the mixtures of our invention are as follows:
menthol having the structure: 
WS 23(copyright) (registered trademark of the Warner Lambert Company) having the structure: 
menthyl succinate having the structure: 
the monomenthyl ether of glycerin having the structure: 
WS 3(copyright) (registered trademark of the Warner Lambert Company) having the structure: 
the compound having the structure: 
the compound having the structure: 
the compound having the structure: 
the compound having the structure: 
the compound having the structure: 
the compound having the structure: 
the compound having the structure: 
the compound having the structure: 
the compound having the structure: 
When dimethyl sulfoxide having the structure: 
is admixed with such xe2x80x9csecond compound(s),xe2x80x9d the resulting mixture as stated, supra, has a highly intensified oral sensory perception effect, for example, a xe2x80x9chighly intensified cooling effectxe2x80x9d or a xe2x80x9chighly intensified hot, burning effect.xe2x80x9d Such effects are highly desirable in the use of certain oral care products such as mouthwashes, toothpastes and the like as set forth, supra. Thus, the following Table I sets forth a comparison of a xe2x80x9ccontrolxe2x80x9d which is a xe2x80x9csecond compoundxe2x80x9d taken alone vs. the mixture of dimethyl sulfoxide with the said xe2x80x9csecond compoundxe2x80x9d:

wherein R11, R12 and R13 each represent hydrogen.
When the second compounds are defined according to the structures: 
R11, R12 and R13 each represents the same or different hydrogen, methyl, ethyl, n-propyl or isopropyl. Such compounds are set forth in U.S. Pat. No. 5,545,424, the specification for which is incorporated by reference herein.
The following Table II sets forth the effect in a screening base, in this case: silica toothpaste base containing 0.4% saccharin of various xe2x80x9csecond compoundsxe2x80x9d in admixture with dimethyl sulfoxide, as follows:
More specifically, our invention includes coolant compositions having intensified and substantive cooling properties, as well as heat sensation-imparting compositions having intensified and substantive heat-imparting properties, consisting essentially of a product produced by the step of admixing dimethyl sulfoxide having the structure: 
with at least one coolant or heat sensation-imparting compound having a formula selected from the group consisting of:
Xxe2x80x94Axe2x80x94H; Xxe2x80x94Axe2x80x94B1; and [Xxe2x80x94Axe2x8ax96]N[B2+N]
wherein
the weight ratio of xe2x80x9ccoolantxe2x80x9d or xe2x80x9cheatingxe2x80x9d compound, dimethyl sulfoxide, is from 1,000:1 up to 3:10 and wherein X represents menthyl having the structure: 
or vanillyl having the structure: 
or a moiety having the structure: 
a moiety having the structure: 
or menthoxy maleyl, succinyl, glutaryl or the like having the structure: 
wherein m is an integer of from 1 up to 4; or n-butyl having the structure: 
or 2,3,4-trimethyl-3-pentyl having the structure: 
or 2,4-dimethyl-3-hexyl having the structure: 
or menthoxy lactyl having the structure: 
wherein A represents a divalent ether or alcohol linkage having the structure: "Brketopenst"O"Brketclosest" or a divalent carbonyl linkage having the structure: 
wherein B1 represents one of the moieties: 
wherein R11, R12 and R13 are each the same or different and each represents hydrogen and C1-C3 lower alkyl, that is, methyl, ethyl, n-propyl or i-propyl; and wherein B2 represents one of the cations:
[NH4+]; [Ca++]; [Na+]; [Mg++]; and/or [K+]
and wherein N represents an integer of 1 or 2.
Examples of the compounds represented by the structure: Xxe2x80x94Axe2x80x94H are as follows: 
Another example of a compound represented by the structure: Xxe2x80x94Axe2x80x94H is the compound having the structure: 
Examples of compounds represented by the structure: Xxe2x80x94Axe2x80x94B1 are as follows: 
(wherein R11, R12 and R13 are the same or different and each represents hydrogen or C1-C3 lower alkyl); 
Examples of compounds represented by the structure: [Xxe2x80x94Axe2x8ax96]N[B2+N] are as follows: 
(wherein N is 1 or 2 and wherein M represents one of the cations:
[NH4+]; [Ca++]; [Na+]; [Mg++]; and/or [K+].
When the dimethyl sulfoxide is in admixture with one of the compounds represented by one of the structures:
Xxe2x80x94Axe2x80x94H; Xxe2x80x94Axe2x80x94B1; and/or [Xxe2x80x94Axe2x8ax96]N[B2+N],
then complexes are formed exemplified by those having the following structures: 
(wherein M is a cation as defined, supra; and N is an integer of 1 or 2); 
(wherein p is an integer of from 1 up to 3); 
Such complexes are shown using the generic formulae: 
Generic reactions to form said complexes are as follows: 
A specific reaction to form such a complex is set forth as follows: 
whereby the complex having the structure: 
is formed.
In each of the consumable articles produced according to our invention, that is, in the beverages, toothpastes, throat lozenges, mouthwashes, dental floss, chewing gums, edible films and chewable pharmaceutical products of our invention, the concentration of dimethyl sulfoxide (on a premixed basis) based on the weight of ultimate product is from about 0.05 up to about 200 ppm. In each of the consumable articles of our invention, the concentration of second compound, that is one of the compounds having one of the structures:
Xxe2x80x94Axe2x80x94H; Xxe2x80x94Axe2x80x94B1; and/or [Xxe2x80x94Axe2x8ax96]N[B2+N]
on a premixed basis, based on the weight of the ultimate product, is from about 2 up to about 10,000 ppm.
An example of a breath freshener film is one produced from pullulan and modified starches containing 5% actives as produced by the Warner Lambert Company. Another example is HERB LEAF(copyright) produced by the Ha-Buri-Fu K.K. Organization of Japan under the trademark HERB LEAF(copyright) (registered trademark of the Ha-Buri-Fu K.K. Organization), specifically described in Japanese Patent No. 1843452, the specification for which is incorporated by reference herein. Other examples of products wherein the compositions of our invention are useful are as follows:
(a) toothpaste as disclosed in Examples 6-10 of U.S. Pat. No. 4,029,759 issued on Jun. 14, 1977, the specification for which is incorporated by reference herein;
(b) chewing gum compositions as set forth in Example 1 at column 10 of U.S. Pat. No. 5,009,893 issued on Apr. 23, 1991, the specification for which is incorporated by reference herein;
(c) hard candy (formed into throat lozenges) as exemplified in Example 4 of U.S. Pat. No. 5,545,424 issued on Aug. 13, 1996, the specification for which is incorporated by reference herein;
(d) mouth rinse formulations as set forth in Examples 3 and 4 of PCT Application No. WO 93/23005 published on Nov. 25, 1993, the specification for which is incorporated by reference herein;
(e) sugarless gums as set forth in Examples 30-37 in Table 7 of PCT Application No. WO 99/13870 published on Mar. 25, 1999, the specification for which is incorporated by reference herein; and
(f) chewing gums as exemplified in Examples 6-10 in Table 3 of PCT Application No. WO 99/13734 published on Mar. 25, 1999, the specification for which is incorporated by reference herein.